Pyrimidin-4-one and pyrimidin-4-thione as fungicide

ABSTRACT

Novel pyrimidin-4-one and pyrimidin-4-thione derivatives of formula I                    
     wherein 
     A is phenyl, thienyl (including all 3 isomers), thiazolyl, pyridyl or pyridazinyl; 
     X is oxygen or sulfur; 
     R 1  is hydrogen, halogen or trimethylsilyl, 
     R 2  is hydrogen, halogen or trimethylsilyl; at least one of R 1  and R 2  is not hydrogen; 
     R 3  is C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkinyl which are unsubstituted or mono to tri-substituted by C 3 -C 6 cycloalkyl, halogen, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; O—C 1 -C 6 alkyl, O—C 2 -C 6 alkenyl, 
     O—C 2 -C 6 alkynyl, which are unsubstituted or mono to tri-substituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 6 alkoxy; N—C 1 -C 6 alkyl; or N═CHC 1 -C 6 alkyl; 
     R 4  is C 1 -C 8 alkyl, C 1 -C 8 alkeanyl, C 1 -C 8 alkinyl which are unsubstituted or mono to tri-substituted by C 3 -C 6 cycloalkyl, halogen, cyano, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkylthio; nitro; —CO—C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; or phenyl, 
     which is unsubstituted or mono to tri-substituted by halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, cyano, nitro, amino, mono-C 1 -C 6 alkylamino, di-C 1 -C 6 alkyl-amino, C 1 -C 6 alkylthio, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or 
     C 1 -C 6 haloalkoxy. The novel compounds have plant-protective properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms, in particular fungi.

The present invention relates to novel pyrimidin-4-one and pyrimidin-4-thione derivatives of formula I, which have pesticidal activity, in particular fungicidal activity,

wherein

A is phenyl, thienyl (including all 3 isomers), thiazolyl, pyridyl or pyridazinyl;

X is oxygen or sulfur;

R₁ is hydrogen, halogen or trimethylsilyl;

R₂ is hydrogen, halogen or trimethylsilyl; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen, C₁-C₆alkoxy or C₁-C₆haloalkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₆alkoxy; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl;

R₄ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen, cyano, C₁-C₆alkoxy or C₁-C₆haloalkoxy; C₁-C₄alkoxy-C₁-C₄alkoxy; C₁-C₄alkoxy-C₁-C₄alkylthio; nitro; —CO—C₁-C₆alkyl; C₃-C₆cycloalkyl; or phenyl, which is unsubstituted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, cyano, nitro, amino, mono-C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylthio, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy.

The invention also relates to the preparation of these compounds, to agrochemical compositions comprising as active ingredient at least one of these compounds, as well as to the use of the active ingredients or compositions for pest control, in particular as fungicides, in agriculture and horticulture.

The compounds I and, optionally, their tautomers may be obtained in the form of their salts. Because the compounds I have at least one basic center they can, for example, form acid addition salts. Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid.

Together with at least one acidic group, the compounds of formula I can also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal salts or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine. Where appropriate, the formation of corresponding internal salts is also possible. Within the scope of this invention, agrochemical acceptable salts are preferred.

Where asymmetrical carbon atoms are present in the compounds of formula I, these compounds are in optically active form. Owing to the presence of double bonds, the compounds can be obtained in the [E] and/or [Z] form. Atropisomerism can also occur. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.

The general terms used hereinabove and hereinbelow have the following meanings, unless otherwise defined:

Alkyl groups on their own or as structural element of other groups such as alkoxy are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl, 3-hexyl, 1-heptyl or 1-octyl.

Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, 1-pentenyl, 1-hexenyl, 1-heptenyl or 1-octenyl. Preferred alkenyl radicals contain 3 to 4 carbon atoms in the chain.

Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl, but-1-yn-3-yl, 1-pentinyl, 1-hexinyl, 1-heptinyl or 1-octinyl. The preferred meaning is propargyl.

Halogen and halo substituents will be understood generally as meaning fluorine, chlorine, bromine or iodine. Fluorine, chlorine or bromine are preferred meanings.

Haloalkyl can contain identical or different halogen atoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.

Cycloalkyl is, depending on the ring size, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cycooctyl.

Preferred compounds are those of formula I, wherein

A is thienyl, including all 3 isomers (subgroup A).

Within the scope of said subgroup A, those compounds of formula I are preferred wherein

R₁ is hydrogen, fluorine, chlorine, bromine or iodine;

R₂ is hydrogen, fluorine, chlorine, bromine or iodine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substitute by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkyoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup B).

A special group within the scope of subgroup B is that of the compounds of formula I, wherein

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₄cycloalkyl, fluorine, chlorine, bromine or C₁-C₄alkoxy; O—C₁-C₆alkyl; O—C₂-C₆alkenyl;

O—C₂-C₆alkynyl; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₄cycloalkyl, fluorine, chlorine, bromine or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine (subgroup C).

A preferred group within the scope of subgroup C is that of the compounds of the formula I, wherein

A is thienyl[2.3-d],

X is oxygen,

R₁ is hydrogen, chlorine or bromine;

R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl;

R₄ is C₂-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which the phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine (subgroup D1).

Another preferred group within the scope of subgroup C is that of compounds of the formula I, wherein

A is thienyl[2.3-d],

X is sulfur,

R₁ is hydrogen, chlorine or bromine;

R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl;

R₄ is C₂-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which the phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine (subgroup D2).

Another preferred group within the scope of subgroup C is that of the compounds of the formula I, wherein

A is thienyl[3.2-d],

X is oxygen,

R₁ is hydrogen, chlorine or bromine;

R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl;

R₄ is C₂-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which the phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine (subgroup E).

Another preferred group of compounds are those of formula I, wherein

A is pyridyl (subgroup F).

Within the scope of said group F, those compounds of formula I are preferred wherein

X is oxygen;

R₁ is hydrogen, fluorine, chlorine, bromine or iodine;

R₂ is hydrogen, fluorine, chlorine, bromine or iodine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to ri-substitute by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup G).

Other preferred group of compounds are those of formula I, wherein

A is phenyl (subgroup H).

Within the scope of said group H, those compounds of formula I are preferred wherein

X is oxygen;

R₁ is hydrogen, fluorine, chlorine, bromine or iodine;

R₂ is hydrogen, fluorine, chlorine, bromine or iodine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup J1).

Another preferred group within the scope of subgroup H is that of compounds of the formula I, wherein

X is sulfur;

R₁ is hydrogen, fluorine, chlorine or bromine;

R₂ is hydrogen, fluorine, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substitute by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup J2).

Other preferred groups of compounds are those of formula I, wherein

A is thiazolyl (subgroup K).

Within the scope of said group K, those compounds of formula I are preferred wherein

X is oxygen;

R₁ is hydrogen, fluorine, chlorine, bromine or iodine;

R₂ is hydrogen, fluorine, chlorine, bromine or iodine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup L).

Another preferred group of compounds are those of formula I, wherein

A is pyridazinyl (subgroup M).

Within the scope of said group M, those compounds of formula I are preferred wherein

X is oxygen;

R₁ is hydrogen, fluorine, chlorine, bromine or iodine;

R₂ is hydrogen, fluorine, chlorine, bromine or iodine; at least one of R₁ and R₂ is not hydrogen;

R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy;

R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkinyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy (subgroup N).

The compounds of formula I can be prepared as follows:

The compounds of formula I are preferably prepared starting from α-amino-β-carboalkoxyheterocycles or α-amino-β-carbocyclic acid heterocycles, some of which, where Het=thienyl, are commercially available (2 isomers). The methyl thiophene-2-amino-3-carboxylate can be prepared, for example, in accordance with Acta Pharm. Suecica 1968, Vol. 5, p.563, according to S. Gronowitz et al. Other heterocycles can be prepared according to instructions in the literature. The synthesis of, for example, ethyl 5-aminothiazole-4-carboxylate and ethyl 5-amino-2-methylthiazole4-carboxylate is described by Golankiewicz et al. in Tetrahedron 1985, 41, 5989. The reaction of the α-amino-β-carboalkoxyheterocycles or α-amino-β-carbocyclic acid heterocycles with amides (R₄CONHR₃) (step 1 in scheme 1) is conveniently carried out in the presence of POCl₃, SOCl₂ or SO₂Cl₂, in solvents, such as ClCH₂CH₂Cl, CHCl₃, CH₂Cl₂, benzene, toluene, hexane, cyclohexane or others in the temperature range from RT to retlux temperature. The resulting amidines (III) either cyclise spontaneously to the pyrimidin-4-ones or were converted into the cyclised products by treatment with bases such as t-Butyl-O—K, NaH, KH, n-BuLi, NaOH, Na₂CO₃ or others in solvents such as THF, dioxane, hexane, toluene, DMSO, DMF, dimethylacetamid or others at temperatures between 20° C. and reflux-temperature.

The replacement of the 4-one group with sulfur to the 4-thione group (step 3 in scheme 1) is carried out by reaction with P₂S₅ or Lawesson-reagent in tetrahydrofurane, dioxane or toluene as solvent in the temperature range of RT to reflux temperature.

The above synthesis route is the first disclosure of how to prepare 3H-thieno[2.3-d]-pyrimidin-4-one derivatives within the structural pattern of formula I herein.

Methods for the preparation of compounds of the general formula I wherein R₁=R₂=hydrogen are described in Chemical Scripta 1981, 18, 135, Synthesis 1977, 180, Chem.Pharm.Bull. 1989, 37,2122 and DE-OS-2411273.

The invention also relates to the intermediates of the formula III, IV and V, and especially to those wherein A represents thienyl[2.3-d].

The introduction of further substituents into the 5-ring of the thienopyrimidin-4-ones may also conveniently be carried out using metallorganic methodology. Thieno[3.2-d]-pyrimidin-4-ones and thieno[2.3-d]pyrimidin-4ones, for example, can be deprotonised selectively in 6-position. Particularly suitable bases for this purpose are lithium diisopropylamide (LDA), lithium cyclohexylisopropylamide (LICA) or secondary butyl lithium/TMEDA. A great number of the radicals R₁ or R₂ indicated above can be introduced by reacting the resulting anions with electrophiles (step 1 in scheme 2), typically Br₂, NBS, F₂, ICl, Cl₂, F⁺ reagents, trimethylsilyl chloride.

The following compounds can likewise be prepared in general accordance with the methods described in scheme 2:

Scheme 3: synthesis of especial thienopypirimidin-4-ones (special methods for the introduction of halogen into thiopene ring)

1-3 molar equivalents of N-bromosuccinimide or N-chlorosuccinimide (or Cl₂ gas or Br₂) are used for halogenation. The solvent used is, for example, pyridine in the temperature range from 0° C. to reflux. The reaction time is 1 to 24 hours.

The described reactions are carried out in per se known manner, e.g. in the presence or absence of a suitable solvent or diluent or of a mixture thereof, if appropriate with cooling, at room temperature or with heating, e.g. in the temperature range from about −20° C. to the boiling temperature of the reaction medium, preferably in the range from about −20° C. to about +150° C. and, if required, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.

Illustrative examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, typically benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers, typically diethyl ether, tert-butylmethyl ether, tetrahydrofuran or dioxane; ketones, typically acetone or methyl ethyl ketone; alcohols, typically methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, typically ethyl acetate or butyl acetate; amides, typically N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitrites, typically acetonitrile; and sulfoxides, typically dimethylsulfoxide. Bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also be used as solvents or diluents.

Suitable bases are, for example, alkali metal hydroxide or alkaline earth metal hydroxide, alkali metal hydride or alkaline earth metal hydride, alkali metal amide or alkaline earth metal amide, alkali metal alkanolate or alkaline earth metal alkanolate, alkali metal carbonate or alkaline earth metal carbonate, alkali metal dialkylamide or alkaline earth metal dialkylamide, or alkali metal alkylsilylamide or alkaline earth metal alkylsilylamide, alkylamines, alkylenediamines, optionally N-alkylated, optionally unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples meriting mention are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyltrimethylammonium hydroxide, and 1,8diazabicyclo[5.4.0]undec-5-ene (DBU).

The compounds of the formula I can also be prepared as follows

The amino carboxylic acidamide of formula VI reacts with the orthoester of formula XIII in the presence or absence of a suitable solvent or diluent, if required in the presence of an acid catalyst at room temperature or with heating, e.g. in the temperature range fromn about 20 to 200° C. Illustrative examples of solvents or diluents are ethers like tert.butylmethylether, tetrahydrofurane, dimethylether, amides like N,N-dimethylformamide or N-methyl-pyrrolidone; sulfoxides, typically dimethylsulfoxid and alcohols like methanol, ethanol, propanol, butanol, ethylene glycol or glycerol. As catalyst can be used hydrogen halides, methanesulfonic acid, triflouromethyl aceticacid, p-toluenesulfonic acid and others in the absence of water. Commonly used bases are sodium hydroxid, potassium hydroxid, sodium hydrogencarbonate, sodium carbonate, sodium hydride, potassium hydride, potassium carbonate and others.

Especially for the thienopyrimidinone, scheme 5 describes the reaction of the aminothiophene-carboxylic-acid amide VIa with the orthoester XIII in the presence or absence of a solvent, if required in the presence of an acid catalyst in the temperature range from 20 to 200° C. The resulting intermediate VIIa is then halogenated in the presence of a solvent at temperatures from 20° C. to reflux. The halogenated intermediate VIIIa is than cyclised in the presence of a base, in the presence or absence of a suitable solvent at temperatures from 20° C. to reflux. Halogenation reagents are typically N-Bromsuccinimide, N-Chlorsuccinimide, N-iodsuccinimide, Chlorgas, Br₂, thionylchloride and others. Preferably solvents used for the halogenation are tert.-butylmethylether, tetrahydrofurane, chloroform, methylenechloride, pyridine and quinoline.

Another alternative is described in scheme 6, in which the amino-carboalkoxy-thiophene of formula IIa reacts with the orthoester XIII to the intermediate IXa, than the compound IXa is transformed to the amidine IIIa and cyclised to the thienopyrimidinone X. The halogenation of X to obtain I.1 is as described in Scheme 3.

The reaction conditions from IIa to IXa is as described in the schemes 4 or 5, as well as the cyclisation from IIIa to X is as described above. The reaction from IXa to IIIa requires as solvent for example tetrahydrofurane, N,N-dimethylformamide or others at a temperature range from 0° C. to reflux.

The scheme 7 describes the reaction of the compound ha with the orthoester XIII to obtain the intermediate IXa, which is converted to the intermediate IIIa and than halogenated to the thiophene XIa. Cyclisation of XIa gives the compound I.1.

The reactions conditions described in process 4 are as described analogously in the schemes 4, 5 or 6.

Scheme 8 describes the alternative route comprising the reaction of the compound IIa with the orthoester XIII to the intermediate IXa, which is halogenated to the intermediate XIIa and than converted to the thiophene XIa. Cyclisation of XIa gives the end product I.1. The reactions conditions are as described in the schemes 4, 5, 6 and 7.

Quinazolinone derivatives having fungicidal properties are known from WO-94/26722 or EP-A-276825 and thienopyrimidincnes are known from WO-97/02262.

Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.

The compounds of formula I can be used in the agricultural sector and related fields as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

The compounds I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Altemaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).

Within the scope of this invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibber plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.

Mixing components which are particularly preferred are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazoie, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-aminopyrimidine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatine, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129 or 2-[α{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime; dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthiodicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper; nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine or validamycin.

Preferred compound for mixing with the above-mentioned mixing components is compound no. 3.30.

Another preferred compound for mixing with the above-mentioned mixing components is compound no. 3.31.

Another preferred compound for mixing with the above-mentioned mixing components is compound no. 3.58.

Another preferred compound for mixing with the above-mentioned mixing components is compound no. 3.59.

Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.

A preferred method of applylng a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are convenientty formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.

The formulation, i.e. the compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant, are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surface active compounds (surfactants).

Suitable carriers and adjuvants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners binding agents or fertilizers. Such carriers are for example described in WO 97/33890.

Further surfactants customarily employed in the art of formulation are known to the expert or can be found in the relevant literature.

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

The following non-limitative Examples illustrate the above-described invention in more detail. Temperatures are given in degrees Celsius. The following abbreviations are used: Et=ethyl; i-propyl=isopropyl; Me=methyl; m.p.=melting point. “NMR” means nuclear magnetic resonance spectrum. MS=mass spectrum. “%” is percent by weight, unless corresponding concentrations are indicated in other units.

PREPARATION EXAMPLES Example P-1 2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide

In a destillation apparatus, a mixture of 1.84 g of 2-aminothiophene-3-carboxylic-acid propylamide and 2.43 g of trimethyl orthovalerate is heated for 2 hours at 130° C. Methanol, which arises during the reaction is directly distilled out of the reaction flask. After cooling, the crude product is purified by column chromatography (eluant:hexane/ethylacetate=1:2). Yield:1.9 g pure 2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide; m.p. 68-70° C.

Example P-2 5-Chloro-2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide

In a sulfonation flask 0.85 g 2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide are added with stirring to 10 ml absolute pyridine. The internal temperature is then raised to 60° C. and 0.5 g of N-chlorosuccinimide (NCS) are added in two portions. After stirring for 1 hour at 60° C., the pyridine is removed in a water jet vacuum. The residue is taken up in ethylacetate and the organic phase is washed twice with water. After drylng of the organic phase, the solvent is removed in a water jet vacuum and the raw material purified by column chromatography over silica gel (eluant:hexane/ethylacetate=3:1). Yield: 0.6 g 5-Chloro-2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide in the form of brownish crystalls; m.p. 110-112° C.

Example P-3 2-n-Butyl-3-n-propyl-3H-thieno[2,3-d]pyrimidin-4-one

In a sulfonation flask, 0.85 g of 2-(1-n-butyl-1-methoxymethyleneamino)-thiophene-3-carboxylicacid propylamide is dissolved in 20 ml of absolute THF and 0.15 g of a ca. 55% NaH dispersion is added in small portions. The mixture is stirred for 15 minutes at room temperature and 1 hour at reflux temperature. Then the solvent is removed in a water jet vacuum and the residue taken up in ethylacetate. The organic phase is washed twice with water and after drying of the organic phase with sodium sulfate, the solvent is removed in a water jet vacuum. The resulting crude product (yleld: 0.8 g of 2-n-butyl-3-n-propyl-3H-thieno[2,3-d]-pyrimidine-4-one in the form of a brown liquid) can be used without further purification for the halogenation step.

Example P-4 2-n-butyl-6-chloro-3-n-propyl-3H-thieno[2,3-d]pyrimidine-4-one

In a sulfonation flask, 0.36 g of 5-Chloro-2-(1-n-butyl-1-methoxymethyleneamino)thiophene-3-carboxylic-acid propylamide is dissolved in 20 ml of absolute THF and 0.085 g of a ca. 55% NaH dispersion is added in one portion. The mixture is stirred for 15 minutes at room temperature and 1 hour at reflux temperature. Then the solvent is removed in a water jet vacuum and the residue taken up in ethylacetate. The organic phase is washed twice with water and after drylng of the organic phase with sodium sulfate, the solvent is removed in a water jet vacuum. The resulting crude product is purified by column chromatography over silica gel (eluant:hexane/ethylacetate=5:1). Yield: 0.2 g 2-n-butyl-6-chloro-3-n-propyl-3H-thieno[2,3-d]pynimidin-4-one in the form of a slightly yellowish powder; m.p. 67-69° C.

Example P-3a 2-n-butyl-3-n-propyl-3H-thieno[2.3-d]pyrimidin-4-one

In a sulfonation flask, 11.0 g (70 mmol) of 2-amino-3-carbomethoxythiophen and 10.9 g (76 mmol) valeric acid propylamide are added to 60 ml 1,2-dichloroethane. Under stirring and at room temperature 7 ml of phosphoroxychloride is slowly added dropwise. After 3 hours at reflux temperature the mixture is poored into ice water and adjusted light alkali with sodium hydrogencarbonat. The resulting mixture is then extracted three times with methylenechloride and the separated organic phase dried over sodium sulfate. The solvent is then removed in a water-jet vacuum.

In a sulfonation flask, the crude product is added to 100 ml of absolute tetrahydrofurane and under stirring 4.36 g (0.1 mol) NaH in 50 ml abs. THF is carefully added. After stirring for 2 hours at reflux temperature, the solvent is removed in a water-jet vacuum and the residue is taken up in ethyl acetate/water. The water-phase is extracted with additionally ethyl acetate. The organic phase is dried over sodium sulfate and the solvent removed in a waterjet vacuum. The crude product is purified by column chromatography over silica gel (eluant:TBME/hexane=1:2). 12.0 g of 2-n-butyl-3-n-propyl-3H-thieno[2.3-d]pyrimidin-4-one are obtained in the form of a yellow powder having a melting point of 70-72° C.

Example P-4a 2-n-butyl-6-chloro-3-n-propyl-3H-thieno-[2.3-d]pyrimidin-4-one

In a sulfonation flask, 2.0 g (8 mmol) of 2-n-butyl-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one are added, with stirring, to 15 ml of absolute pyridine. The internal temperature is then raised to 80° C. and then 1.87 g (14 mmol) of N-chlorosuccinimide (NCS) are added in smallish portions. After stirring for 3 hours at 90° C. 1.0 g of NCS is added and the mixture is stirred another 3 hours at 90° C. The pyridine is removed in a water-jet vacuum and the crude product so obtained is purified by column chromatography over silica gel (eluant:n-hexane/tert.butylmethylether=3:1), giving 0.9 g of 2-n-butyl-6-chloro-3-propyl-3H-thieno-[2.3-d]pyrimidin-4-one in the form of a beige powder having a melting point of 67-69° C.

TABLE 1 A = Phenyl

phys. data cmpd. No. R₁ R₂ R₃ R₄ m.p. ° C. 1.1 6-Br H Me Me 1.2 6-Cl H Me Et 1.3 6-Br H Me n-Propyl 1.4 6-Cl H Me n-Propyl 1.5 H 7-Cl Me n-Propyl 1.6 6-Br H Me n-Butyl 1.7 6-Cl H Me n-Butyl 1.8 H 7-Cl Me n-Butyl 1.9 6-Br H Me i-Butyl 1.10 6-Cl H Me i-Butyl 1.11 6-Br H Me n-Pentyl 1.12 6-Br H Me

1.13 6-Cl H Me

1.14 6-Br H Et Me 1.15 6-Cl H Et Et 1.16 6-Br H Et n-Propyl 1.17 6-Cl H Et n-Propyl 1.18 H 7-Cl Et n-Propyl 1.19 6-Br H Et n-Butyl 1.20 6-Cl H Et n-Butyl 1.21 H 7-Cl Et n-Butyl 1.22 6-Br H Et i-Butyl 1.23 6-Cl H Et i-Butyl 1.24 6-Br H Et n-Pentyl 1.25 6-Br H Et

1.26 6-Cl H Et

1.27 6-Br H n-Propyl Me 1.28 6-Cl H n-Propyl Et 1.29 6-Br H n-Propyl n-Propyl 1.30 6-Cl H n-Propyl n-Propyl 1.31 H 7-Cl n-Propyl n-Propyl 1.32 H 7-I n-Propyl n-Propyl 1.33 6-Br H n-Propyl

1.34 6-Cl H n-Propyl

1.35 H 7-Cl n-Propyl

1.36 6-Br H n-Propyl n-Butyl 130-135 1.37 6-Cl H n-Propyl n-Butyl 1.38 H 7-Cl n-Propyl n-Butyl 1.39 H 7-I n-Propyl n-Butyl 1.40 6-Br H n-Propyl i-Butyl 1.41 6-Cl H n-Propyl i-Butyl 1.42 6-Br H n-Propyl

1.43 6-Cl H n-Propyl

1.44 H 7-Cl n-Propyl

1.45 6-Br H n-Propyl

1.46 6-Cl H n-Prpyl

1.47 6-Br H n-Propyl Cyclobutyl 1.48 6-Br H n-Propyl n-Pentyl 1.49 6-Cl H n-Propyl n-Pentyl 1.50 H 7-Cl n-Propyl n-Pentyl 1.51 6-Br H n-Propyl Cyclopentyl 1.52 6-Br H n-Propyl n-Hexyl 1.53 6-Br H n-Propyl Cyclohexyl 1.54 6-Br H n-Propyl Phenyl 1.55 6-Br H n-Propyl 4-Chloro- phenyl 1.56 6-Cl H n-Propyl 4-Chloro- phenyl 1.57 6-Br H n-Propyl 4-Phenoxy- phenyl 1.58 6-Br H n-Butyl Me 1.59 6-Cl H n-Butyl Et 1.60 6-Br H n-Butyl n-Propyl 1.61 6-Cl H n-Butyl n-Propyl 1.62 H 7-Cl n-Butyl n-Propyl 1.63 H 7-I n-Butyl n-Propyl 1.64 6-Br H n-Butyl

1.65 6-Cl H n-Butyl

1.66 H 7-Cl n-Butyl

1.67 6-Br H n-Butyl n-Butyl 1.68 6-Cl H n-Butyl n-Butyl 1.69 H 7-Cl n-Butyl n-Butyl 1.70 H 7-I n-Butyl n-Butyl 1.71 6-Br H n-Butyl i-Butyl 1.72 6-Cl H n-Butyl i-Butyl 1.73 6-Br H n-Butyl

1.74 6-Cl H n-Butyl

1.75 H 7-Cl n-Butyl

1.76 6-Br H n-Butyl

1.77 6-Cl H n-Butyl

1.78 6-Br H n-Butyl Cyclobutyl 1.79 6-Br H n-Butyl n-Pentyl 1.80 6-Cl H n-Butyl n-Pentyl 1.81 H 7-Cl n-Butyl n-Pentyl 1.82 6-Br H n-Butyl Cyclopentyl 1.83 6-Br H n-Butyl n-Hexyl 1.84 6-Br H n-Butyl Cyclohexyl 1.85 6-Br H n-Butyl Phenyl 1.86 6-Br H n-Butyl 4-Chloro- phenyl 1.87 6-Cl H n-Butyl 4-Chloro- phenyl 1.88 6-Br H n-Butyl 4-Phenoxy- phenyl 1.89 6-Br H i-Butyl n-Propyl 1.90 6-Cl H i-Butyl n-Propyl 1.91 6-Br H i-Butyl n-Butyl 1.92 6-Cl H i-Butyl n-Butyl 1.93 6-Br H

n-Propyl 1.94 6-Cl H

n-Propyl 1.95 6-Br H

n-Propyl 1.96 6-Br H

n-Butyl 1.97 6-Br H n-Pentyl Me 1.98 6-Cl H n-Pentyl Et 1.99 6-Br H n-Pentyl n-Propyl 1.100 6-Cl H n-Pentyl n-Propyl 1.101 H 7-Cl n-Pentyl n-Propyl 1.102 H 7-I n-Pentyl n-Propyl 1.103 6-Br H n-Pentyl

1.104 6-Cl H n-Pentyl

1.105 H 7-Cl n-Pentyl

1.106 6-Br H n-Pentyl n-Butyl 1.107 6-Cl H n-Pentyl n-Butyl 1.108 H 7-Cl n-Pentyl n-Butyl 1.109 H 7-I n-Pentyl n-Butyl 1.110 6-Br H n-Pentyl i-Butyl 1.111 6-Cl H n-Pentyl i-Butyl 1.112 6-Br H n-Pentyl

1.113 6-Cl H n-Pentyl

1.114 H 7-Cl n-Pentyl

1.115 6-Br H n-Pentyl

1.116 6-Cl H n-Pentyl

1.117 6-Br H n-Pentyl Cyclobutyl 1.118 6-Br H n-Pentyl n-Pentyl 1.119 6-Cl H n-Pentyl n-Pentyl 1.120 H 7-Cl n-Pentyl n-Pentyl 1.121 6-Br H n-Pentyl Cyclopentyl 1.122 6-Br H n-Pentyl n-Hexyl 1.123 6-Br H n-Pentyl Cyclohexyl 1.124 6-Br H n-Pentyl Phenyl 1.125 6-Br H n-Pentyl 4-Chloro- phenyl 1.126 6-Cl H n-Pentyl 4-Chloro- phenyl 1.127 6-Br H n-Pentyl 4-Phenoxy- phenyl 1.128 6-Br H OEt Me 1.129 6-Cl H OEt Et 1.130 6-Br H OEt n-Propyl 1.131 6-Cl H OEt n-Propyl 1.132 H 7-Cl OEt n-Propyl 1.133 H 7-I OEt n-Propyl 1.134 6-Br H OEt

1.135 6-Cl H OEt

1.136 H 7-Cl OEt

1.137 6-Br H OEt n-Butyl 1.138 6-Cl H OEt n-Butyl 1.139 H 7-Cl OEt n-Butyl 1.140 H 7-I OEt n-Butyl 1.141 6-Br H OEt i-Butyl 1.142 6-Cl H OEt i-Butyl 1.143 6-Br H OEt

1.144 6-Cl H OEt

1.145 H 7-Cl OEt

1.146 6-Br H OEt

1.147 6-Cl H OEt

1.148 6-Br H OEt Cyclobutyl 1.149 6-Br H OEt n-Pentyl 1.150 6-Cl H OEt n-Pentyl 1.151 H 7-Cl OEt n-Pentyl 1.152 6-Br H OEt Cyclopentyl 1.153 6-Br H OEt n-Hexyl 1.154 6-Br H OEt Cyclohexyl 1.155 6-Br H OEt Phenyl 1.156 6-Br H OEt 4-Chloro- phenyl 1.157 6-Cl H OEt 4-Chloro- phenyl 1.158 6-Br H OEt 4-Phenoxy- phenyl 1.159 6-Br H O-n-Propyl Me 1.160 6-Cl H O-n-Propyl Et 1.161 6-Br H O-n-Propyl n-Propyl 1.162 6-Cl H O-n-Propyl n-Propyl 1.163 H 7-Cl O-n-Propyl n-Propyl 1.164 H 7-I O-n-Propyl n-Propyl 1.165 6-Br H O-n-Propyl

1.166 6-Cl H O-n-Propyl

1.167 H 7-Cl O-n-Propyl

1.168 6-Br H O-n-Propyl n-Butyl 1.169 6-Cl H O-n-Propyl n-Butyl 1.170 H 7-Cl O-n-Propyl n-Butyl 1.171 H 7-I O-n-Propyl n-Butyl 1.172 6-Br H O-n-Propyl i-Butyl 1.173 6-Cl H O-n-Propyl i-Butyl 1.174 6-Br H O-n-Propyl

1.175 6-Cl H O-n-Propyl

1.176 H 7-Cl O-n-Propyl

1.177 6-Br H O-n-Propyl

1.178 6-Cl H O-n-Propyl

1.179 6-Br H O-n-Propyl Cyclobutyl 1.180 6-Br H O-n-Propyl n-Pentyl 1.181 6-Cl H o-n-Propyl n-Pentyl 1.182 H 7-Cl O-n-Propyl n-Pentyl 1.183 6-Br H O-n-Propyl Cyclopentyl 1.184 6-Br H O-n-Prpyl n-Hexyl 1.185 6-Br H O-n-Prpyl Cyclohexyl 1.186 6-Br H O-n-Prpyl Phenyl 1.187 6-Br H O-n-Prpyl 4-Chloro- phenyl 1.188 6-Cl H O-n-Prpyl 4-Chloro- phenyl 1.189 6-Br H O-n-Prpyl 4-Phenoxy- phenyl 1.190 6-Br H Et CH₂OMe 1.191 6-Cl H Et CH₂OMe 1.192 6-Br H n-Prpyl CH₂OMe 1.193 6-Cl H n-Prpyl CH₂OMe 1.194 H 7-Cl n-Prpyl CH₂OMe 1.195 6-Br H n-Butyl CH₂OMe 1.196 6-Cl H n-Butyl CH₂OMe 1.197 6-Br H

CH₂OMe 1.198 6-Br H n-Pentyl CH₂OMe 1.199 6-Br H Et CH₂OEt 1.200 6-Cl H Et CH₂OEt 1.201 6-Br H n-Propyl CH₂OEt 1.202 6-Cl H n-Propyl CH₂OEt 1.203 H 7-Cl n-Propyl CH₂OEt 1.204 6-Br H n-Butyl CH₂OEt 1.205 6-Cl H n-Butyl CH₂OEt 1.206 6-Br H

CH₂OEt 1.207 6-Br H n-Pentyl CH₂OEt 1.208 6-Br H n-Propyl CH₂CN 1.209 6-Br H n-Butyl CH₂CN 1.210 6-Br H n-Propyl t-Butyl 1.211 6-Br H n-Propyl t-Butyl 1.212 6-Cl H n-Propyl CF₃ 1.213 6-Br H n-Propyl CF₃ 1.214 6-Br H n-Butyl CF₃

TABELLE 2 A = Pyridyl

cmpd. phys. data No. R₁ R₂ R₃ R₄ m.p. ° C. 2.1 6-Br H Me Me 2.2 6-Cl H Me Et 2.3 6-Br H Me n-Propyl 2.4 6-Cl H Me n-Propyl 2.5 6-Br H Me n-Butyl 2.6 6-Cl H Me n-Butyl 2.7 6-Br H Me i-Butyl 2.8 6-Cl H Me i-Butyl 2.9 6-Br H Me n-Pentyl 2.10 6-Br H Me

2.11 6-Cl H Me

2.12 6-Br H Et Me 2.13 6-Cl H Et Et 2.14 6-Br H Et n-Propyl 2.15 6-Cl H Et n-Propyl 2.16 6-Br H Et n-Butyl 2.17 6-Cl H Et n-Butyl 2.18 6-Br H Et i-Butyl 2.19 6-Cl H Et i-Butyl 2.20 6-Br H Et n-Pentyl 2.21 6-Br H Et

2.22 6-Cl H Et

2.23 6-Br H n-Propyl Me 2.24 6-Cl H n-Propyl Et 2.25 6-Br H n-Propyl n-Propyl 2.26 6-Cl H n-Propyl n-Propyl 2.27 7-I H n-Propyl n-Propyl 2.28 6-Br H n-Propyl

2.29 6-Cl H n-Propyl

2.30 6-Br H n-Propyl n-Butyl Oil, ¹H-NMR 2.31 6-Cl H n-Propyl n-Butyl 2.32 6-I H n-Propyl n-Butyl 2.33 6-Br H n-Propyl i-Butyl 2.34 6-Cl H n-Propyl i-Butyl 2.35 6-Br H n-Propyl

2.36 6-Cl H n-Propyl

2.37 6-Br H n-Propyl

2.38 6-Cl H n-Propyl

2.39 6-Br H n-Propyl Cyclobutyl 2.40 6-Br H n-Propyl n-Pentyl 2.41 6-Cl H n-Propyl n-Pentyl 2.42 6-Br H n-Propyl Cyclopentyl 2.43 6-Br H n-Propyl n-Hexyl 2.44 6-Br H n-Propyl Cyclohexyl 2.45 6-Br H n-Propyl Phenyl 2.46 6-Br H n-Propyl 4-Chloro- phenyl 2.47 6-Cl H n-Propyl 4-Chloro- phenyl 2.48 6-Br H n-Propyl 4-Phenoxy- phenyl 2.49 6-Br H n-Butyl Me 2.50 6-Cl H n-Butyl Et 2.51 6-Br H n-Butyl n-Propyl 2.52 6-Cl H n-Butyl n-Propyl 2.53 H 7-Cl n-Butyl n-Propyl 2.54 H 7-I n-Butyl n-Propyl 2.55 6-Br H n-Butyl

2.56 6-Cl H n-Butyl

2.57 H 7-Cl n-Butyl

2.58 6-Br H n-Butyl n-Butyl 2.59 6-Cl H n-Butyl n-Butyl 2.60 6-I H n-Butyl n-Butyl 2.61 6-Br H n-Butyl i-Butyl 2.62 6-Cl H n-Butyl i-Butyl 2.63 6-Br H n-Butyl

2.64 6-Cl H n-Butyl

2.65 6-I H n-Butyl

2.66 6-Br H n-Butyl

2.67 6-Cl H n-Butyl

2.68 6-Br H n-Butyl Cyclobutyl 2.69 6-Br H n-Butyl n-Pentyl 2.70 6-Cl H n-Butyl n-Pentyl 2.71 6-Br H n-Butyl Cyclopentyl 2.72 6-Br H n-Butyl n-Hexyl 2.73 6-Br H n-Butyl Cyclohexyl 2.74 6-Br H n-Butyl Phenyl 2.75 6-Br H n-Butyl 4-Chloro- phenyl 2.76 6-Cl H n-Butyl 4-Chloro- phenyl 2.77 6-Br H n-Butyl 4-Phenoxy- phenyl 2.78 6-Br H i-Butyl n-Propyl 2.79 6-Cl H i-Butyl n-Propyl 2.80 6-Br H i-Butyl n-Butyl 2.81 6-Cl H i-Butyl n-Butyl 2.82 6-Br H

n-Propyl 2.83 6-Cl H

n-Propyl 2.84 6-Br H

n-Propyl 2.85 6-Br H

n-Butyl 2.86 6-Br H n-Pentyl Me 2.87 6-Cl H n-Pentyl Et 2.88 6-Br H n-Pentyl n-Propyl 2.89 6-Cl H n-Pentyl n-Propyl 2.90 6-Br H n-Pentyl

2.91 6-Cl H n-Pentyl

2.92 6-Br H n-Pentyl n-Butyl 2.93 6-Cl H n-Pentyl n-Butyl 2.94 6-I H n-Pentyl n-Butyl 2.95 6-Br H n-Pentyl i-Butyl 2.96 6-Cl H n-Pentyl i-Butyl 2.97 6-Br H n-Pentyl

2.98 6-Cl H n-Pentyl

2.99 6-Br H n-Pentyl

2.100 6-Cl H n-Pentyl

2.101 6-Br H n-Pentyl Cyclobutyl 2.102 6-Br H n-Pentyl n-Pentyl 2.103 6-Cl H n-Pentyl n-Pentyl 2.104 6-Br H n-Pentyl Cyclopentyl 2.105 6-Br H n-Pentyl n-Hexyl 2.106 6-Br H n-Pentyl Cyclohexyl 2.107 6-Br H n-Pentyl Phenyl 2.108 6-Br H n-Pentyl 4-Chloro- phenyl 2.109 6-Cl H n-Pentyl 4-Chloro- phenyl 2.110 6-Br H n-Pentyl 4-Phenoxy- phenyl 2.111 6-Br H OEt Me 2.112 6-Cl H OEt Et 2.113 6-Br H OEt n-Propyl 2.114 6-Cl H OEt n-Propyl 2.115 6-Br H OEt

2.116 6-Cl H OEt

2.117 6-Br H OEt n-Butyl 2.118 6-Cl H OEt n-Butyl 2.119 6-I H OEt n-Butyl 2.120 6-Br H OEt i-Butyl 2.121 6-Cl H OEt i-Butyl 2.122 6-Br H OEt

2.123 6-Cl H OEt

2.124 6-Br H OEt

2.125 6-Cl H OEt

2.126 6-Br H OEt Cyclobutyl 2.127 6-Br H OEt n-Pentyl 2.128 6-Cl H OEt n-Pentyl 2.129 6-Br H OEt Cyclopentyl 2.130 6-Br H OEt n-Hexyl 2.131 6-Br H OEt Cyclohexyl 2.132 6-Br H OEt Phenyl 2.133 6-Br H OEt 4-Chloro- phenyl 2.134 6-Cl H OEt 4-Chloro- phenyl 2.135 6-Br H OEt 4-Phenoxy- phenyl 2.136 6-Br H O-n-Propyl Me 2.137 6-Cl H O-n-Propyl Et 2.138 6-Br H O-n-Propyl n-Propyl 2.139 6-Cl H O-n-Propyl n-Propyl 2.140 6-Br H O-n-Propyl

2.141 6-Cl H O-n-Propyl

2.142 6-Br H O-n-Propyl n-Butyl 2.143 6-Cl H O-n-Propyl n-Butyl 2.144 6-Br H O-n-Propyl i-Butyl 2.145 6-Cl H O-n-Propyl i-Butyl 2.146 6-Br H O-n-Propyl

2.147 6-Cl H O-n-Propyl

2.148 6-Br H O-n-Propyl

2.149 6-Cl H O-n-Propyl

2.150 6-Br H O-n-Propyl Cyclobutyl 2.151 6-Br H O-n-Propyl n-Pentyl 2.152 6-Cl H O-n-Propyl n-Pentyl 2.153 6-Br H O-n-Propyl Cyclopentyl 2.154 6-Br H O-n-Propyl n-Hexyl 2.155 6-Br H O-n-Propyl Cyclohexyl 2.156 6-Br H O-n-Propyl Phenyl 2.157 6-Br H O-n-Propyl 4-Chloro- phenyl 2.158 6-Cl H O-n-Propyl 4-Chloro- phenyl 2.159 6-Br H O-n-Propyl 4-Phenoxy- phenyl 2.160 6-Br H Et CH₂OMe 2.161 6-Cl H Et CH₂OMe 2.162 6-Br H n-Propyl CH₂OMe 2.163 6-Cl H n-Propyl CH₂OMe 2.164 6-Br H n-Butyl CH₂OMe 2.165 6-Cl H n-Butyl CH₂OMe 2.166 6-Br H

CH₂OMe 2.167 6-Br H n-Pentyl CH₂OMe 2.168 6-Br H Et CH₂OEt 2.169 6-Cl H Et CH₂OEt 2.170 6-Br H n-Propyl CH₂OEt 2.171 6-Cl H n-Propyl CH₂OEt 2.172 6-Br H n-Butyl CH₂OEt 2.173 6-Cl H n-Butyl CH₂OEt 2.174 6-Br H

CH₂OEt 2.175 6-Br H n-Pentyl CH₂OEt 2.176 6-Br H n-Propyl CH₂CN 2.177 6-Br H n-Butyl CH₂CN 2.178 6-Br H n-Propyl t-Butyl 2.179 6-Br H n-Propyl t-Butyl 2.180 6-Br H n-Propyl CF₃ 2.181 6-Br H n-Butyl CF₃

TABELLE 3 A = Thienyl[2.3-d]

cmpd. phys. data No. R₁ R₂ R₃ R₄ m.p. ° C. 3.1 Cl H Me Me 139-141 3.2 Cl H Me Et 3.3 Br H Me n-Propyl 3.4 Cl H Me n-Propyl 3.5 Br H Me n-Butyl 3.6 Cl H Me n-Butyl 63-65 3.7 Br H Me i-Butyl 3.8 Cl H Me i-Butyl 87-89 3.9 Br H Me n-Pentyl 3.10 Br H Me

3.11 Cl H Me

3.12 Br H Et Me 3.13 Cl H Et Et 3.14 Br H Et n-Propyl 3.15 Cl H Et n-Propyl 80-82 3.16 Br H Et n-Butyl 3.17 Cl H Et n-Butyl Oil, ¹H-NMR 3.18 Br H Et i-Butyl 3.19 Cl H Et i-Butyl 3.20 Br H Et n-Pentyl 3.21 Br H Et

3.22 Cl H Et

3.23 Br H n-Propyl Me 3.24 Cl H n-Propyl Et 3.25 Br H n-Propyl n-Propyl 3.26 Cl H n-Propyl n-Propyl 74-76 3.27 I H n-Propyl n-Propyl 3.28 Br H n-Propyl

3.29 Cl H n-Propyl

3.30 Br H n-Propyl n-Butyl 63-66 3.31 Cl H n-Propyl n-Butyl 67-69 3.32 I H n-Propyl n-Butyl 3.33 Br H n-Propyl i-Butyl 3.34 Cl H n-Propyl i-Butyl Oil, ¹H-NMR 3.35 Br H n-Propyl

3.36 Cl H n-Propyl

Oil, ¹H-NMR 3.37 Br H n-Propyl

3.38 Cl H n-Propyl

3.39 Br H n-Propyl Cyclobutyl 3.40 Br H n-Propyl n-Pentyl 3.41 Cl H n-Propyl n-Pentyl 3.42 Br H n-Propyl Cyclopentyl 3.43 Br H n-Propyl n-Hexyl 3.44 Br H n-Propyl Cyclohexyl 3.45 Br H n-Propyl Phenyl 3.46 Br H n-Propyl 4-Chloro- phenyl 3.47 Cl H n-Propyl 4-Chloro- 126-128 phenyl 3.48 Br H n-Propyl 4-Phenoxy- phenyl 3.49 Br H n-Butyl Me 3.50 Cl H n-Butyl Et 3.51 Br H n-Butyl n-Propyl 3.52 Cl H n-Butyl n-Propyl Oil 3.53 I H n-Butyl n-Propyl 3.54 I H n-Butyl n-Propyl 3.55 Br H n-Butyl

3.56 Cl H n-Butyl

54-56 3.57 I H n-Butyl

3.58 Br H n-Butyl n-Butyl Oil 3.59 Cl H n-Butyl n-Butyl 57-58 3.60 I H n-Butyl n-Butyl 3.61 Br H n-Butyl i-Butyl 3.62 Cl H n-Butyl i-Butyl 3.63 Br H n-Butyl

3.64 Cl H n-Butyl

3.65 I H n-Butyl

3.66 Br H n-Butyl

3.67 Cl H n-Butyl

3.68 Br H n-Butyl Cyclobutyl 3.69 Br H n-Butyl n-Pentyl 3.70 Cl H n-Butyl n-Pentyl 3.71 Br H n-Butyl Cyclopentyl 3.72 Br H n-Butyl n-Hexyl 3.73 Br H n-Butyl Cyclohexyl 3.74 Cl H n-Butyl Phenyl 3.75 Br H n-Butyl 4-Chloro- phenyl 3.76 Cl H n-Butyl 4-Chloro- phenyl 3.77 Br H n-Butyl 4-Phenoxy- phenyl 3.78 Br H i-Butyl n-Propyl 3.79 Cl H i-Butyl n-Propyl Oil, ¹H-NMR 3.80 Br H i-Butyl n-Butyl 3.81 Cl H i-Butyl n-Butyl 3.82 Br H

n-Propyl 3.83 Cl H

n-Propyl 3.84 Cl H

n-Propyl 3.85 Br H

n-Butyl 3.86 Br H n-Pentyl Me 3.87 Cl H n-Pentyl Et 3.88 Br H n-Pentyl n-Propyl 3.89 Cl H n-Pentyl n-Propyl 3.90 Br H n-Pentyl

3.91 Cl H n-Pentyl

3.92 Br H n-Pentyl n-Butyl 3.93 Cl H n-Pentyl n-Butyl 3.94 I H n-Pentyl n-Butyl 3.95 Br H n-Pentyl i-Butyl 3.96 Cl H n-Pentyl i-Butyl 3.97 Br H n-Pentyl

3.98 Cl H n-Pentyl

3.99 Br H n-Pentyl

3.100 Cl H n-Pentyl

3.101 Cl H n-Pentyl Cyclobutyl 3.102 Br H n-Pentyl n-Pentyl 3.103 Cl H n-Pentyl n-Pentyl 3.104 Cl H n-Pentyl Cyclopentyl 3.105 Br H n-Pentyl n-Hexyl 3.106 Cl H n-Pentyl Cyclohexyl 3.107 Br H n-Pentyl Phenyl 3.108 Br H n-Pentyl 4-Chloro- phenyl 3.109 Cl H n-Pentyl 4-Chloro- phenyl 3.110 Br H n-Pentyl 4-Phenoxy- phenyl 3.111 Br H OEt Me 3.112 Cl H OEt Et 3.113 Br H OEt n-Propyl 3.114 Cl H OEt n-Propyl 3.115 Br H OEt

3.116 Cl H OEt

3.117 Br H OEt n-Butyl 75-77 3.118 Cl H OEt n-Butyl 66-69 3.119 I H OEt n-Butyl 3.120 Br H OEt i-Butyl 3.121 Cl H OEt i-Butyl 3.122 Br H OEt

3.123 Cl H OEt

3.124 Br H OEt

3.125 Cl H OEt

3.126 Br H OEt Cyclobutyl 3.127 Br H OEt n-Pentyl 3.128 Cl H OEt n-Pentyl 3.129 Br H OEt Cyclopentyl 3.130 Br H OEt n-Hexyl 3.131 Br H OEt Cyclohexyl 3.132 Br H OEt Phenyl 3.133 Br H OEt 4-Chloro- phenyl 3.134 Cl H OEt 4-Chloro- phenyl 3.135 Cl H OEt 4-Phenoxy- phenyl 3.136 Br H O-n-Propyl Me 3.137 Cl H O-n-Propyl Et 3.138 Br H O-n-Propyl n-Propyl 3.139 Cl H O-n-Propyl n-Propyl 3.140 Br H O-n-Propyl

3.141 Cl H O-n-Propyl

3.142 Br H O-n-Propyl n-Butyl 3.143 Cl H O-n-Propyl n-Butyl 3.144 Br H O-n-Propyl i-Butyl 3.145 Cl H O-n-Propyl i-Butyl 3.146 Br H O-n-Propyl

3.147 Cl H O-n-Propyl

3.148 Br H O-n-Propyl

3.149 Cl H O-n-Propyl

3.150 Br H O-n-Propyl Cyclobutyl 3.151 Br H O-n-Propyl n-Pentyl 3.152 Cl H O-n-Propyl n-Pentyl 3.153 Br H O-n-Propyl Cyclopentyl 3.154 Cl H O-n-Propyl n-Hexyl 3.155 Br H O-n-Propyl Cyclohexyl 3.156 Cl H O-n-Propyl Phenyl 3.157 Br H O-n-Propyl 4-Chloro- phenyl 3.158 Cl H O-n-Propyl 4-Chloro- phenyl 3.159 Br H O-n-Propyl 4-Phenoxy- phenyl 3.160 Br H Et CH₂OMe 3.161 Cl H Et CH₂OMe 3.162 Br H n-Propyl CH₂OMe 3.163 Cl H n-Propyl CH₂OMe Oil, ¹H-NMR 3.164 Br H n-Butyl CH₂OMe 3.165 Cl H n-Butyl CH₂OMe 3.166 Br H

CH₂OMe 3.167 Br H n-Pentyl CH₂OMe 3.168 Br H Et CH₂OEt 3.169 Cl H Et CH₂OEt 3.170 Br H n-Propyl CH₂OEt 3.171 Cl H n-Propyl CH₂OEt 40-41 3.172 Br H n-Butyl CH₂OEt 3.173 Cl H n-Butyl CH₂OEt 3.174 Br H

CH₂OEt 3.175 Br H n-Pentyl CH₂OEt 3.176 Br H n-Propyl CH₂CN 3.177 Cl H n-Butyl CH₂CN 3.178 Br H n-Propyl t-Butyl 3.179 Cl H n-Propyl t-Butyl 3.180 Br H n-Propyl CF₃ 3.181 Cl H n-Butyl CF₃ 3.182 Cl H n-Pentyl CF₃ 3.183 Cl Cl n-Propyl n-Propyl 3.184 Cl Cl n-Propyl n-Butyl 3.185 Br Br n-Propyl n-Butyl 3.186 Br Br n-Butyl n-Butyl

TABELLE 4 A = Thienyl[3.2-d]

Cmpd. No. R₁ R₂ R₃ R₄ phys. data 4.1 Br H Me Me 4.2 H Cl Me Et 4.3 Br H Me n-Propyl 4.4 H Cl Me n-Propyl 4.5 H Cl Me n-Propyl 4.6 Br H Me n-Butyl 4.7 H Cl Me n-Butyl 4.8 H Cl Me n-Butyl 4.9 Br H Me i-Butyl 4.10 H Cl Me i-Butyl 4.11 Br H Me n-Pentyl 4.12 Br H Me

4.13 H Cl Me

4.14 Br H Et Me 4.15 H Cl Et Et 4.16 Br H Et n-Propyl 4.17 H Cl Et n-Propyl 4.18 H Cl Et n-Propyl 4.19 Br H Et n-Butyl 4.20 H Cl Et n-Butyl 4.21 H Cl Et n-Butyl 4.22 Br H Et i-Butyl 4.23 H Cl Et i-Butyl 4.24 Br H Et n-Pentyl 4.25 Br H Et

4.26 H Cl Et

4.27 Br H n-Propyl Me 4.28 H Cl n-Propyl Et 4.29 Br H n-Propyl n-Propyl 4.30 H Cl n-Propyl n-Propyl 4.31 H Cl n-Propyl n-Propyl 4.32 H I n-Propyl n-Propyl 4.33 Br H n-Propyl

4.34 H Cl n-Propyl

4.35 H Cl n-Propyl

4.36 Br H n-Propyl n-Butyl 120-121 4.37 H Cl n-Propyl n-Butyl 4.38 H Cl n-Propyl n-Butyl 4.39 H I n-Propyl n-Butyl 4.40 Br H n-Propyl i-Butyl 4.41 H Cl n-Propyl i-Butyl 4.42 Br H n-Propyl

4.43 H Cl n-Porpyl

4.44 H Cl n-Propyl

4.45 H Cl n-Propyl

4.46 H Cl n-Propyl

4.47 Br H n-Propyl Cyclobutyl 4.48 Br H n-Propyl n-Pentyl 4.49 H Cl n-Propyl n-Pentyl 4.50 H Cl n-Propyl n-Pentyl 4.51 Br H n-Propyl Cyclopentyl 4.52 Br H n-Propyl n-Hexyl 4.53 Br H n-Propyl Cyclohexyl 4.54 Br H n-Propyl Phenyl 4.55 Br H n-Propyl 4-Chloro- phenyl 4.55 H Cl n-Propyl 4-Chloro- phenyl 4.56 Br H n-Propyl 4-Phenoxy- phenyl 4.57 Br H n-Butyl Me 4.58 H Cl n-Butyl Et 4.59 Br H n-Butyl n-Propyl 4.60 H Cl n-Butyl n-Propyl 4.61 H Cl n-Butyl n-Propyl 4.62 H I n-Butyl n-Propyl 4.62 Br H n-Butyl

4.63 H Cl n-Butyl

4.64 H Cl n-Butyl

4.65 Br H n-Butyl n-Butyl 4.66 H Cl n-Butyl n-Butyl 4.67 H Cl n-Butyl n-Butyl 4.68 H I n-Butyl n-Butyl 4.69 Br H n-Butyl i-Butyl 4.70 H Cl n-Butyl i-Butyl 4.71 Br H n-Butyl

4.72 H Cl n-Butyl

4.73 H Cl n-Butyl

4.74 Br H n-Butyl

4.75 H Cl n-Butyl

4.76 Br H n-Butyl Cyclobutyl 4.77 Br H n-Butyl n-Pentyl 4.78 H Cl n-Butyl n-Pentyl 4.79 H Cl n-Butyl n-Pentyl 4.80 Br H n-Butyl Cyclopentyl 4.81 Br H n-Butyl n-Hexyl 4.82 Br H n-Butyl Cyclohexyl 4.83 Br H n-Butyl Phenyl 4.84 Br H n-Butyl 4-Chloro- phenyl 4.85 H Cl n-Butyl 4-Chloro- phenyl 4.86 Br H n-Butyl 4-Phenoxy- phenyl 4.87 Br H i-Butyl n-Propyl 4.88 H Cl i-Butyl n-Propyl 4.89 Br H i-Butyl n-Butyl 4.90 H Cl i-Butyl n-Butyl 4.91 Br H

n-Propyl 4.92 H Cl

n-Propyl 4.93 Br H

n-Propyl 4.94 Br H

n-Butyl 4.95 Br H n-Pentyl Me 4.96 H Cl n-Pentyl Et 4.97 Br H n-Pentyl n-Propyl 4.98 Cl H n-Pentyl n-Propyl 4.99 H Cl n-Pentyl n-Propyl 4.100 H I n-Pentyl n-Propyl 4.101 Br H n-Pentyl

4.102 H Cl n-Pentyl

4.103 H Cl n-Pentyl

4.104 Br H n-Pentyl n-Butyl 4.105 H Cl n-Pentyl n-Butyl 4.106 H Cl n-Pentyl n-Butyl 4.107 H I n-Pentyl n-Butyl 4.108 Br H n-Pentyl i-Butyl 4.109 H Cl n-Pentyl i-Butyl 4.110 Br H n-Pentyl

4.111 H Cl n-Pentyl

4.112 H Cl n-Pentyl

4.113 Br H n-Pentyl

4.114 H Cl n-Pentyl

4.115 Br H n-Pentyl Cyclobutyl 4.116 Br H n-Pentyl n-Pentyl 4.117 Cl Cl n-Pentyl n-Pentyl 4.118 H Cl n-Pentyl n-Pentyl 4.119 Br H n-Pentyl Cyclopentyl 4.120 Br H n-Pentyl n-Hexyl 4.121 Br H n-Pentyl Cyclohexyl 4.122 Br H n-Pentyl Phenyl 4.123 Br H n-Pentyl 4-Chloro- phenyl 4.124 H Cl n-Pentyl 4-Chloro- phenyl 4.125 Br H n-Pentyl 4-Phenoxy- phenyl 4.126 Br H OEt Me 4.127 Cl H OEt Et 4.128 Br H OEt n-Propyl 4.129 H Cl OEt n-Propyl 4.130 H Cl OEt n-Propyl 4.131 H I OEt n-Propyl 4.132 Br H OEt

4.133 H Cl OEt

4.134 H Cl OEt

4.135 Br H OEt n-Butyl 4.136 H Cl OEt n-Butyl 4.137 H Cl OEt n-Butyl 4.138 H I OEt n-Butyl 4.139 Br H OEt i-Butyl 4.140 H Cl OEt i-Butyl 4.141 Br H OEt

4.142 H Cl OEt

4.143 H Cl OEt

4.144 Br H OEt

4.145 H Cl OEt

4.146 Br H OEt Cyclobutyl 4.147 Br H OEt n-Pentyl 4.148 H Cl OEt n-Pentyl 4.149 H Cl OEt n-Pentyl 4.150 Br H OEt Cyclopentyl 4.151 Br H OEt n-Hexyl 4.152 Br H OEt Cyclohexyl 4.153 Br H OEt Phenyl 4.154 Br H OEt 4-Chloro- phenyl 4.155 Cl OEt 4-Chloro- phenyl 4.156 Br H OEt 4-Phenoxy- phenyl 4.157 Br H O-n-Propyl Me 4.158 H Cl O-n-Propyl Et 4.159 Br H O-n-Propyl n-Propyl 4.160 H Cl O-n-Propyl n-Propyl 4.161 H Cl O-n-Propyl n-Propyl 4.162 H I O-n-Propyl n-Propyl 4.163 Br H O-n-Propyl

4.164 H Cl O-n-Propyl

4.165 H Cl O-n-Propyl

4.166 Br H O-n-Propyl n-Butyl 4.167 H Cl O-n-Propyl n-Butyl 4.168 H Cl O-n-Propyl n-Butyl 4.169 H H O-n-Propyl n-Butyl 4.170 Br H O-n-Propyl i-Butyl 4.171 H Cl O-n-Propyl i-Butyl 4.172 Br H O-n-Propyl

4.173 H Cl O-n-Propyl

4.174 H Cl O-n-Propyl

4.175 Br H O-n-Propyl

4.176 H Cl O-n-Propyl

4.177 Br H O-n-Propyl Cyclobutyl 4.178 Br H O-n-Propyl n-Pentyl 4.179 H Cl O-n-Propyl n-Pentyl 4.180 H Cl O-n-Propyl n-Pentyl 4.181 Br H O-n-Propyl Cyclopentyl 4.182 Br H O-n-Propyl n-Hexyl 4.183 Br H O-n-Propyl Cyclohexyl 4.184 Br H O-n-Propyl Phenyl 4.185 Br H O-n-Propyl 4-Chloro- phenyl 4.186 H Cl O-n-Propyl 4-Chloro- phenyl 4.187 Br H O-n-Propyl 4-Phenoxy- phenyl 4.188 Br H Et CH₂OMe 4.189 H Cl Et CH₂OMe 4.190 Br H n-Propyl CH₂OMe 4.191 H Cl n-Propyl CH₂OMe 4.192 H Cl n-Propyl CH₂OMe 4.193 Br H n-Butyl CH₂OMe 4.194 H Cl n-Butyl CH₂OMe 4.195 Br H

CH₂OMe 4.195 Br H n-Pentyl CH₂OMe 4.196 Br H Et CH₂OEt 4.197 H Cl Et CH₂OEt 4.198 Br H n-Propyl CH₂OEt 4.199 H Cl n-Propyl CH₂OEt 4.200 H Cl n-Propyl CH₂OEt 4.201 Br H n-Butyl CH₂OEt 4.202 H Cl n-Butyl CH₂OEt 4.203 Br H

CH₂OEt 4.204 Br H n-Pentyl CH₂OEt 4.205 Br H n-Propyl CH₂CN 4.206 Br H n-Butyl CH₂CN 4.207 Br H n-Propyl t-Butyl 4.208 Br H n-Propyl t-Butyl 4.209 H Cl n-Propyl CF₃ 4.210 Br H n-Propyl CF₃ 4.211 H Cl n-Butyl CF₃ 4.212 Br H n-Butyl CF₃ 4.213 Cl Cl n-Propyl n-Propyl 4.214 Cl Cl n-Propyl n-Butyl 4.215 Br Br n-Propyl n-Butyl 4.216 Br Br n-Butyl n-Butyl

TABELLE 5 A = Thiazolyl

Cmpd. No. R₁ R₃ R₄ phys. data 5.1 H Et n-Propyl 5.2 H n-Propyl n-Propyl 5.3 H n-Propyl n-Butyl 5.4 H n-Butyl n-Butyl 5.5 Me n-Propyl n-Propyl 5.6 Me n-Propyl n-Butyl 5.7 Me n-Butyl n-Butyl 5.8 H n-Propyl Phenyl

TABELLE 6 A = Phenyl

phys. data cmpd. No. R₁ R₂ R₃ R₄ m.p. ° C. 6.1 6-Br H Me Me 6.2 6-Cl H Me Et 6.3 6-Br H Me n-Propyl 6.4 6-Cl H Me n-Propyl 6.5 H 7-Cl Me n-Propyl 6.6 6-Br H Me n-Butyl 6.7 6-Cl H Me n-Butyl 6.8 H 7-Cl Me n-Butyl 6.9 6-Br H Me i-Butyl 6.10 6-Cl H Me i-Butyl 6.11 6-Br H Me n-Pentyl 6.12 6-Br H Me

6.13 6-Cl H Me

6.14 6-Br H Et Me 6.15 6-Cl H Et Et 6.16 6-Br H Et n-Propyl 6.17 6-Cl H Et n-Propyl 6.18 H 7-Cl Et n-Propyl 6.19 6-Br H Et n-Butyl 6.20 6-Cl H Et n-Butyl 6.21 H 7-Cl Et n-Butyl 6.22 6-Br H Et i-Butyl 6.23 6-Cl H Et i-Butyl 6.24 6-Br H Et n-Pentyl 6.25 6-Br H Et

6.26 6-Cl H Et

6.27 6-Br H n-Propyl Me 6.28 6-Cl H n-Propyl Et 6.29 6-Br H n-Propyl n-Propyl Oil, ¹H-NMR 6.30 6-Cl H n-Propyl n-Propyl 6.31 H 7-Cl n-Propyl n-Propyl 6.32 H 7-I n-Propyl n-Propyl 6.33 6-Br H n-Propyl

6.34 6-Cl H n-Propyl

6.35 H 7-Cl n-Propyl

6.36 6-Br H n-Propyl n-Butyl 6.37 6-Cl H n-Propyl n-Butyl 6.38 H 7-Cl n-Propyl n-Butyl 6.39 H 7-I n-Propyl n-Butyl 6.40 6-Br H n-Propyl i-Butyl 6.41 6-Cl H n-Propyl i-Butyl 6.42 6-Br H n-Propyl

6.43 6-Cl H n-Propyl

6.44 H 7-Cl n-Propyl

6.45 6-Br H n-Propyl

6.46 6-Cl H n-Prpyl

6.47 6-Br H n-Propyl Cyclobutyl 6.48 6-Br H n-Propyl n-Pentyl 6.49 6-Cl H n-Propyl n-Pentyl 6.50 H 7-Cl n-Propyl n-Pentyl 6.51 6-Br H n-Propyl Cyclopentyl 6.52 6-Br H n-Propyl n-Hexyl 6.53 6-Br H n-Propyl Cyclohexyl 6.54 6-Br H n-Propyl Phenyl 6.55 6-Br H n-Propyl 4-Chloro- phenyl 6.56 6-Cl H n-Propyl 4-Chloro- phenyl 6.57 6-Br H n-Propyl 4-Phenoxy- phenyl 6.58 6-Br H n-Butyl Me 6.59 6-Cl H n-Butyl Et 6.60 6-Br H n-Butyl n-Propyl 6.61 6-Cl H n-Butyl n-Propyl 6.62 H 7-Cl n-Butyl n-Propyl 6.63 H 7-I n-Butyl n-Propyl 6.64 6-Br H n-Butyl

6.65 6-Cl H n-Butyl

6.66 H 7-Cl n-Butyl

6.67 6-Br H n-Butyl n-Butyl 6.68 6-Cl H n-Butyl n-Butyl 6.69 H 7-Cl n-Butyl n-Butyl 6.70 H 7-I n-Butyl n-Butyl 6.71 6-Br H n-Butyl i-Butyl 6.72 6-Cl H n-Butyl i-Butyl 6.73 6-Br H n-Butyl

6.74 6-Cl H n-Butyl

6.75 H 7-Cl n-Butyl

6.76 6-Br H n-Butyl

6.77 6-Cl H n-Butyl

6.78 6-Br H n-Butyl Cyclobutyl 6.79 6-Br H n-Butyl n-Pentyl 6.80 6-Cl H n-Butyl n-Pentyl 6.81 H 7-Cl n-Butyl n-Pentyl 6.82 6-Br H n-Butyl Cyclopentyl 6.83 6-Br H n-Butyl n-Hexyl 6.84 6-Br H n-Butyl Cyclohexyl 6.85 6-Br H n-Butyl Phenyl 6.86 6-Br H n-Butyl 4-Chloro- phenyl 6.87 6-Cl H n-Butyl 4-Chloro- phenyl 6.88 6-Br H n-Butyl 4-Phenoxy- phenyl 6.89 6-Br H i-Butyl n-Propyl 6.90 6-Cl H i-Butyl n-Propyl 6.91 6-Br H i-Butyl n-Butyl 6.92 6-Cl H i-Butyl n-Butyl 6.93 6-Br H

n-Propyl 6.94 6-Cl H

n-Propyl 6.95 6-Br H

n-Propyl 6.96 6-Br H

n-Butyl 6.97 6-Br H n-Pentyl Me 6.98 6-Cl H n-Pentyl Et 6.99 6-Br H n-Pentyl n-Propyl 6.100 6-Cl H n-Pentyl n-Propyl 6.101 H 7-Cl n-Pentyl n-Propyl 6.102 H 7-I n-Pentyl n-Propyl 6.103 6-Br H n-Pentyl

6.104 6-Cl H n-Pentyl

6.105 H 7-Cl n-Pentyl

6.106 6-Br H n-Pentyl n-Butyl 6.107 6-Cl H n-Pentyl n-Butyl 6.108 H 7-Cl n-Pentyl n-Butyl 6.109 H 7-I n-Pentyl n-Butyl 6.110 6-Br H n-Pentyl i-Butyl 6.111 6-Cl H n-Pentyl i-Butyl 6.112 6-Br H n-Pentyl

6.113 6-Cl H n-Pentyl

6.114 H 7-Cl n-Pentyl

6.115 6-Br H n-Pentyl

6.116 6-Cl H n-Pentyl

6.117 6-Br H n-Pentyl Cyclobutyl 6.118 6-Br H n-Pentyl n-Pentyl 6.119 6-Cl H n-Pentyl n-Pentyl 6.120 H 7-Cl n-Pentyl n-Pentyl 6.121 6-Br H n-Pentyl Cyclopentyl 6.122 6-Br H n-Pentyl n-Hexyl 6.123 6-Br H n-Pentyl Cyclohexyl 6.124 6-Br H n-Pentyl Phenyl 6.125 6-Br H n-Pentyl 4-Chloro- phenyl 6.126 6-Cl H n-Pentyl 4-Chloro- phenyl 6.127 6-Br H n-Pentyl 4-Phenoxy- phenyl 6.128 6-Br H OEt Me 6.129 6-Cl H OEt Et 6.130 6-Br H OEt n-Propyl 6.131 6-Cl H OEt n-Propyl 6.132 H 7-Cl OEt n-Propyl 6.133 H 7-I OEt n-Propyl 6.134 6-Br H OEt

6.135 6-Cl H OEt

6.136 H 7-Cl OEt

6.137 6-Br H OEt n-Butyl 6.138 6-Cl H OEt n-Butyl 6.139 H 7-Cl OEt n-Butyl 6.140 H 7-I OEt n-Butyl 6.141 6-Br H OEt i-Butyl 6.142 6-Cl H OEt i-Butyl 6.143 6-Br H OEt

6.144 6-Cl H OEt

6.145 H 7-Cl OEt

6.146 6-Br H OEt

6.147 6-Cl H OEt

6.148 6-Br H OEt Cyclobutyl 6.149 6-Br H OEt n-Pentyl 6.150 6-Cl H OEt n-Pentyl 6.151 H 7-Cl OEt n-Pentyl 6.152 6-Br H OEt Cyclopentyl 6.153 6-Br H OEt n-Hexyl 6.154 6-Br H OEt Cyclohexyl 6.155 6-Br H OEt Phenyl 6.156 6-Br H OEt 4-Chloro- phenyl 6.157 6-Cl H OEt 4-Chloro- phenyl 6.158 6-Br H OEt 4-Phenoxy- phenyl 6.159 6-Br H O-n-Propyl Me 6.160 6-Cl H O-n-Propyl Et 6.161 6-Br H O-n-Propyl n-Propyl 6.162 6-Cl H O-n-Propyl n-Propyl 6.163 H 7-Cl O-n-Propyl n-Propyl 6.164 H 7-l O-n-Propyl n-Propyl 6.165 6-Br H O-n-Propyl

6.166 6-Cl H O-n-Propyl

6.167 H 7-Cl O-n-Propyl

6.168 6-Br H O-n-Propyl n-Butyl 6.169 6-Cl H O-n-Propyl n-Butyl 6.170 H 7-Cl O-n-Propyl n-Butyl 6.171 H 7-I O-n-Propyl n-Butyl 6.172 6-Br H O-n-Propyl i-Butyl 6.173 6-Cl H O-n-Propyl i-Butyl 6.174 6-Br H O-n-Propyl

6.175 6-Cl H O-n-Propyl

6.176 H 7-Cl O-n-Propyl

6.177 6-Br H O-n-Propyl

6.178 6-Cl H O-n-Propyl

6.179 6-Br H O-n-Propyl Cyclobutyl 6.180 6-Br H O-n-Propyl n-Pentyl 6.181 6-Cl H O-n-Propyl n-Pentyl 6.182 H 7-Cl O-n-Propyl n-Pentyl 6.183 6-Br H O-n-Propyl Cyclopentyl 6.184 6-Br H O-n-Prpyl n-Hexyl 6.185 6-Br H O-n-Prpyl Cyclohexyl 6.186 6-Br H O-n-Prpyl Phenyl 6.187 6-Br H O-n-Prpyl 4-Chloro- phenyl 6.188 6-Cl H O-n-Prpyl 4-Chloro- phenyl 6.189 6-Br H O-n-Prpyl 4-Phenoxy- phenyl 6.190 6-Br H Et CH₂OMe 6.191 6-Cl H Et CH₂OMe 6.192 6-Br H n-Prpyl CH₂OMe 6.193 6-Cl H n-Prpyl CH₂OMe 6.194 H 7-Cl n-Prpyl CH₂OMe 6.195 6-Br H n-Butyl CH₂OMe 6.196 6-Cl H n-Butyl CH₂OMe 6.197 6-Br H

CH₂OMe 6.198 6-Br H n-Pentyl CH₂OMe 6.199 6-Br H Et CH₂OEt 6.200 6-Cl H Et CH₂OEt 6.201 6-Br H n-Propyl CH₂OEt 6.202 6-Cl H n-Propyl CH₂OEt 6.203 H 7-Cl n-Propyl CH₂OEt 6.204 6-Br H n-Butyl CH₂OEt 6.205 6-Cl H n-Butyl CH₂OEt 6.206 6-Br H

CH₂OEt 6.207 6-Br H n-Pentyl CH₂OEt 6.208 6-Br H n-Propyl CH₂CN 6.209 6-Br H n-Butyl CH₂CN 6.210 6-Br H n-Propyl t-Butyl 6.211 6-Br H n-Propyl t-Butyl 6.212 6-Cl H n-Propyl CF₃ 6.213 6-Br H n-Propyl CF₃ 6.214 6-Br H n-Butyl CF₃

TABELLE 7 A = Thienyl[2.3-d]

phys. data cmpd. No. R₁ R₂ R₃ R₄ m.p. ° C. 7.1 Br H Me Me 7.2 Cl H Me Et 7.3 Br H Me n-Propyl 7.4 Cl H Me n-Propyl 7.5 Br H Me n-Butyl 7.6 Cl H Me n-Butyl 113-114 7.7 Br H Me i-Butyl 7.8 Cl H Me i-Butyl 7.9 Br H Me n-Pentyl 7.10 Br H Me

7.11 Cl H Me

7.12 Br H Et Me 7.13 Cl H Et Et 7.14 Br H Et n-Propyl 7.15 Cl H Et n-Propyl 7.16 Br H Et n-Butyl 7.17 Cl H Et n-Butyl 7.18 Br H Et i-Butyl 7.19 Cl H Et i-Butyl 7.20 Br H Et n-Pentyl 7.21 Br H Et

7.22 Cl H Et

7.23 Br H n-Propyl Me 7.24 Cl H n-Propyl Et 7.25 Br H n-Propyl n-Propyl 7.26 Cl H n-Propyl n-Propyl 7.27 I H n-Propyl n-Propyl 7.28 Br H n-Propyl

7.29 Cl H n-Propyl

7.30 Br H n-Propyl n-Butyl 7.31 Cl H n-Propyl n-Butyl Oil, ¹H-NMR 7.32 I H n-Propyl n-Butyl 7.33 Br H n-Propyl i-Butyl 7.34 Cl H n-Propyl i-Butyl 57-60 7.35 Br H n-Propyl

7.36 Cl H n-Propyl

7.37 Br H n-Propyl

7.38 Cl H n-Propyl

7.39 Br H n-Propyl Cyclobutyl 7.40 Br H n-Propyl n-Pentyl 7.41 Cl H n-Propyl n-Pentyl 7.42 Br H n-Propyl Cyclopentyl 7.43 Br H n-Propyl n-Hexyl 7.44 Br H n-Propyl Cyclohexyl 7.45 Br H n-Propyl Phenyl 7.46 Br H n-Propyl 4-Chloro- phenyl 7.47 Cl H n-Propyl 4-Chloro- phenyl 7.48 Br H n-Propyl 4-Phenoxy- phenyl 7.49 Br H n-Butyl Me 7.50 Cl H n-Butyl Et 7.51 Br H n-Butyl n-Propyl 7.52 Cl H n-Butyl n-Propyl 7.53 I H n-Butyl n-Propyl 7.54 I H n-Butyl n-Propyl 7.55 Br H n-Butyl

7.56 Cl H n-Butyl

7.57 I H n-Butyl

7.58 Br H n-Butyl n-Butyl 7.59 Cl H n-Butyl n-Butyl 7.60 I H n-Butyl n-Butyl 7.61 Br H n-Butyl i-Butyl 7.62 Cl H n-Butyl i-Butyl 7.63 Br H n-Butyl

7.64 Cl H n-Butyl

7.65 I H n-Butyl

7.66 Br H n-Butyl

7.67 Cl H n-Butyl

7.68 Br H n-Butyl Cyclobutyl 7.69 Br H n-Butyl n-Pentyl 7.70 Cl H n-Butyl n-Pentyl 7.71 Br H n-Butyl Cyclopentyl 7.72 Br H n-Butyl n-Hexyl 7.73 Br H n-Butyl Cyclohexyl 7.74 Cl H n-Butyl Phenyl 7.75 Br H n-Butyl 4-Chloro- phenyl 7.76 Cl H n-Butyl 4-Chloro- phenyl 7.77 Br H n-Butyl 4-Phenoxy- phenyl 7.78 Br H i-Butyl n-Propyl 7.79 Cl H i-Butyl n-Propyl 7.80 Br H i-Butyl n-Butyl 7.81 Cl H i-Butyl n-Butyl 7.82 Br H

n-Propyl 7.83 Cl H

n-Propyl 7.84 Cl H

n-Propyl 7.85 Br H

n-Butyl 7.86 Br H n-Pentyl Me 7.87 Cl H n-Pentyl Et 7.88 Br H n-Pentyl n-Propyl 7.89 Cl H n-Pentyl n-Propyl 7.90 Br H n-Pentyl

7.91 Cl H n-Pentyl

7.92 Br H n-Pentyl n-Butyl 7.93 Cl H n-Pentyl n-Butyl 7.94 I H n-Pentyl n-Butyl 7.95 Br H n-Pentyl i-Butyl 7.96 Cl H n-Pentyl i-Butyl 7.97 Br H n-Pentyl

7.98 Cl H n-Pentyl

7.99 Br H n-Pentyl

7.100 Cl H n-Pentyl

7.101 Cl H n-Pentyl Cyclobutyl 7.102 Br H n-Pentyl n-Pentyl 7.103 Cl H n-Pentyl n-Pentyl 7.104 Cl H n-Pentyl Cyclopentyl 7.105 Br H n-Pentyl n-Hexyl 7.106 Cl H n-Pentyl Cyclohexyl 7.107 Br H n-Pentyl Phenyl 7.108 Br H n-Pentyl 4-Chloro- phenyl 7.109 Cl H n-Pentyl 4-Chloro- phenyl 7.110 Br H n-Pentyl 4-Phenoxy- phenyl 7.111 Br H OEt Me 7.112 Cl H OEt Et 7.113 Br H OEt n-Propyl 7.114 Cl H OEt n-Propyl 7.115 Br H OEt

7.116 Cl H OEt

7.117 Br H OEt n-Butyl 7.118 Cl H OEt n-Butyl 7.119 I H OEt n-Butyl 7.120 Br H OEt i-Butyl 7.121 Cl H OEt i-Butyl 7.122 Br H OEt

7.123 Cl H OEt

7.124 Br H OEt

7.125 Cl H OEt

7.126 Br H OEt Cyclobutyl 7.127 Br H OEt n-Pentyl 7.128 Cl H OEt n-Pentyl 7.129 Br H OEt Cyclopentyl 7.130 Br H OEt n-Hexyl 7.131 Br H OEt Cyclohexyl 7.132 Br H OEt Phenyl 7.133 Br H OEt 4-Chloro- phenyl 7.134 Cl H OEt 4-Chloro- phenyl 7.135 Cl H OEt 4-Phenoxy- phenyl 7.136 Br H O-n-Propyl Me 7.137 Cl H O-n-Propyl Et 7.138 Br H O-n-Propyl n-Propyl 7.139 Cl H O-n-Propyl n-Propyl 7.140 Br H O-n-Propyl

7.141 Cl H O-n-Propyl

7.142 Br H O-n-Propyl n-Butyl 7.143 Cl H O-n-Propyl n-Butyl 7.144 Br H O-n-Propyl i-Butyl 7.145 Cl H O-n-Propyl i-Butyl 7.146 Br H O-n-Propyl

7.147 Cl H O-n-Propyl

7.148 Br H O-n-Propyl

7.149 Cl H O-n-Propyl

7.150 Br H O-n-Propyl Cyclobutyl 7.151 Br H O-n-Propyl n-Pentyl 7.152 Cl H O-n-Propyl n-Pentyl 7.153 Br H O-n-Propyl Cyclopentyl 7.154 Cl H O-n-Propyl n-Hexyl 7.155 Br H O-n-Propyl Cyclohexyl 7.156 Cl H O-n-Propyl Phenyl 7.157 Br H O-n-Propyl 4-Chloro- phenyl 7.158 Cl H O-n-Propyl 4-Chloro- phenyl 7.159 Br H O-n-Propyl 4-Phenoxy- phenyl 7.160 Br H Et CH₂OMe 7.161 Cl H Et CH₂OMe 7.162 Br H n-Propyl CH₂OMe 7.163 Cl H n-Propyl CH₂OMe 7.164 Br H n-Butyl CH₂OMe 7.165 Cl H n-Butyl CH₂OMe 7.166 Br H

CH₂OMe 7.167 Br H n-Pentyl CH₂OMe 7.168 Br H Et CH₂OEt 7.169 Cl H Et CH₂OEt 7.170 Br H n-Propyl CH₂OEt 7.171 Cl H n-Propyl CH₂OEt 7.172 Br H n-Butyl CH₂OEt 7.173 Cl H n-Butyl CH₂OEt 7.174 Br H

CH₂OEt 7.175 Br H n-Pentyl CH₂OEt 7.176 Br H n-Propyl CH₂CN 7.177 Cl H n-Butyl CH₂CN 7.178 Br H n-Propyl t-Butyl 7.179 Cl H n-Propyl t-Butyl 7.180 Br H n-Propyl CF₃ 7.181 Cl H n-Butyl CF₃ 7.182 Cl H n-Pentyl CF₃ 7.183 Cl Cl n-Propyl n-Propyl 7.184 Cl Cl n-Propyl n-Butyl 7.185 Br Br n-Propyl n-Butyl 7.186 Br Br n-Butyl n-Butyl

Examples for specific formulations-combination are as disclosed e.g. in WO 97/33890, e.g. for wettable powders, emulsifiable concentrates, dusts, extruder granules, coated granules, solutions and suspension concentrates.

BIOLOGICAL EXAMPLES Fungidical Actions Example B-1

Action Against Colletotrichum lagenarium on Cucumbers

After a growth period of 2 weeks, cucumber plants are sprayed with an aqueous spray mixture (concentration 0.002%) prepared from a wettable powder formulation of the test compound and infected 2 days later with a spore suspension (1.5×10⁵ spores/ml) of the fungus and incubated for 36 hours at 23° C. and high humidity. Incubation is then continued at normal humidity and c. 22° C. Evaluation of the fungal infestation is made 8 days after infection.

The compounds of the Tables 1-7 show good to excellent activity, preferably the compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34.

Example B-2

Residual-Drotective Action Against Venturia inaequalis on Apples

Apple cuttings with fresh shoots 10 to 20 cm long are sprayed to drip point with a spray mixture (0.02% a.i.) prepared from a wettable powder formulation of the test compound. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90 to 100% relative humidity and stood in a greenhouse for a further 10 days at 20 to 24° C. Evaluation of the fungal infestation is made 12 days after infection.

Compounds of Tables 1-7 show good activity, preferably the compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34.

Example B-3

Action Against Erysiphe graminis on Barley

a) Residual-Drotective Action

Barley plants about 8 cm in height are sprayed to drip point with a spray mixture (0.02% a.i.) prepared from a wettable powder formulation of the test compound, and the treated plants are dusted with conidia of the fungus 3 to 4 hours later. The infected plants are stood in a greenhouse at 22° C. Evaluation of the fungal infection is made 12 days after infection.

b) Systemic Action

Barley plants about 8 cm in height are drenched with an aqueous spray mixture (0.002% a.i., based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the growing parts of the plants. The treated plants are dusted 48 hours later with conidia of the fungus. The infected plants are then stood in a greenhouse at 22° C. Evaluation of the fungal infestation is made 12 days after infection.

Compared with the control plants, infestation of the plants treated with compounds of formula I from Tables 1-7, for example the compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 is 20% or less.

Example B-4

Action Against Podosphaera leucotricha on Apple Shoots

Apple cuttings with fresh shoots about 15 cm long are sprayed with a spray mixture (0.06% a.i.). The plants are infected 24 hours later with a conidia suspension of the fungus and stood in a climatic chamber at 70% relative humidity and 20° C. Evaluation of the fugal infestation is made 12 days after infection.

Compounds of Tables 1-7 show good activity. The following compounds exhibit especially strong efficacy: 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 (0-5% infestation).

Example B-5

Action Against Plasmopara viticola on Vines

a) Residual-preventive action: Vine cuttings of the Chasselas variety are raised in a greenhouse. At the 10-leat stage, 3 plants are sprayed with a spray mixture (200 ppm a.i.). After the spray coating has dried, the plants are infected uniformly on the underside of the leaves with a spore suspension of the fungus. The plants are then kept in a humidity chamber for 8 days, after which time marked symptoms of disease are observed on the control plants. The number and size of the infected areas on the untreated plants act as an indicator of the efficacy of the tested compounds.

b) Curative action: Vine cuttings of the Chasselas variety are raised in a greenhouse and sprayed at the 10-leaf stage on the underside of the leaves with a spore suspension of Plasmopara viticola. After 24 hours in the humidity chamber, the plants are sprayed with a spray mixture (200 ppm a.i.). The plants are then kept for another 7 days in the humidity chamber. After this time the control plants exhibit symptoms of the disease. The number and size of the infected areas on the untreated plants act as an indicator of the efficacy of the tested compounds.

Compounds of Tables 1-7 show good efficacy, preferably the compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34.

Example B-6

Action Against Uncinula necator on Vines

5 week old vine cuttings are sprayed with a spray mixture (200 ppm a.i.) prepared from a wettable powder formulation of the test compound. The plants are infected 24 hours later by conidias from strongly infested vine leafs that are shaken off over the test plants. The plants are then incubated at 26° C. and 60% relative humidity. The evaluation of the fungal infestation is made ca. 14 days after infection.

Compared with the control plants, infestation of the plants treated with compounds of formula I from the Tables 1-7, for example the compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 is 20% or less. 

What is claimed is:
 1. A compound of formula I

wherein A is thlenyl (including all 3 isomers): X is oxygen or sulfur; R₁ is hydrogen, halogen or trimethylsilyl; R₂ is hydrogen, halogen or trimethylsilyl; at least one of R₁ and R₂ is not hydrogen; R₃ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen, C₁-C₆alkoxy or C₁-C₆haloalkoxy, O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₆alkoxy; N—C₁-C₆alkyl: or N═CHC₁-C₆alkyl; R₄ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₈cycloalkyl, halogen, cyano, C₁-C₆alkoxy or C₁-C₈ahaloalkoxy; nitro; —CO—C₁-C₈alkyl; C₃-C₆cycloalkyl; or phenyl, which is unsubstituted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, cyano, nitro, amino, mono-C₁-C₆alkylamino, di-C₁-C₆alkylamino, C₁-C₈alkylthio, phenyl or phenoxy and in which the phenyl part is unsubstftuted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy.
 2. A compounds of formula I according to claim 1 wherein R₁ is hydrogen, fluorine, chlorine, bromine or iodine; R₂ is hydrogen, fluorine, chlorine, bromine or iodine, at least one of R₁ anld R₂ is not hydrogen; R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalky, halogen or C₁-C₄alkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₁-C₆cycloalkyl, halogen or C₁-C₄alkoxy; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl; R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkynyl which are unsubstituted or mono to tri-substituted by C₁-C₆cycloalkyl, halogen or C₁-C₄alkyoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy.
 3. A compound of formula I according to claim 2, wherein R₃ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₄cycloalkyl, fluorine, chlorine, bromine or C₁-C₄alkoxy; O—C₁-C₆alkyl; O—C₂-C₆alkenyl; O—C₂-C₆alkynyl: N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl; R₄ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl which are unsubstituted or manno to tri-substituted by C₃-C₄cycloalkyl, fluorine, chlorine, bromine or C₁-C₄alkoxy; or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄halo-alkoxy, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine.
 4. A compound of the formula I according to claim 3, wherein A is thienyl[2.3-d], X is oxygen, R₁ is hydrogen, chlorine or bromine; R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen; R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl; R₄ is C₂-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine.
 5. A compound of the formula I according to claim 3, wherein A is thienyl[2.3-d], X is sulfur, R₁ is hydrogen, chlorine or bromine; R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen; R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl; R₄ is C₁-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine.
 6. A compound of the formula I according to claim 3, wherein A is thienyl[3.2-d], X is oxygen, R₁ is hydrogen, chlorine or bromine; R₂ is hydrogen, chlorine or bromine; at least one of R₁ and R₂ is not hydrogen; R₃ is C₃-C₅alkyl or O—C₁-C₄alkyl; R₄ is C₂-C₅alkyl or phenyl which is unsubstituted or mono to tri-substituted by fluorine, chlorine, bromine, C₁-C₄alkyl or phenoxy and in which phenoxy is unsubstituted or mono to tri-substituted by fluorine, chlorine or bromine.
 7. A composition for controlling and preventing pests, wherein the active ingredient is a compound as claimed in claim 1 together with a suitable carrier.
 8. A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula I as claimed in claim 1 to plants, to parts thereof or to the locus thereof.
 9. A method according to claim 8 wherein the phytopathogenic microorganism is a fungal organism.
 10. A method for the preparation of a compound of formula I according to claim 1, which comprises a) converting an α-amino-β-carboalkoxyheterocycle of formula II, wherein R₁ and R₂ have the meanings stated for formula I and R is hydrogen, C₁-C₆alkyl,

with POCl₃ in the presence of a solvent and R₄CONHR₃ into an amidine of formula III, wherein R₃ and R₄ have the meanings stated for formula I

b) and treating the amidine, in the presence of a solvent and in the presence or absence of a base, and obtaining, with ring closure, the pyrimidin-4-one derivative of formula IV

c) reacting an amino carboxylic acidamide of formula VI

wherein A, R₁, R₂ and R₃ have the meanings stated for formula I with an orthoester of formula XIII

wherein R₄ has the meaning stated for formula I and R₅ is C₁-C₅alkyl, in the presence or absence of a solvent, in the presence or absence of an acid catalyst at 20-200° C., and obtaining the pyrimidin-4-one derivative of formula IV; and d) If the intermediate VII is formed

treating the compound VII in the presence of a solvent and in the presence or absence of a base, and obtaining with ring closure the pyrimidin-4one derivative of formula IV.
 11. A compound of formula III

wherein A is thienyl[2.3-d] or thienyl[3.2-d]; R₁ is hydrogen, halogen or trimethylsilyl; R₂ is hydrogen, halogen or trimethylsilyl; and at least one of R₁ and R₂ is not hydrogen; R₃ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen, C₁-C₆alkoxy or C₁-C₆haloalkoxy; O—C₁-C₆alkyl, O—C₂-C₆alkenyl, O—C₂-C₆alkynyl, which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen or C₁-C₆alkoxy; N—C₁-C₆alkyl; or N═CHC₁-C₆alkyl; R₄ is C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl which are unsubstituted or mono to tri-substituted by C₃-C₆cycloalkyl, halogen, cyano, C₁-C₆alkoxy or C₁-C₆haloalkoxy; nitro; —CO—C₁-C₆alkyl; C₃-C₆cycloalkyl; or phenyl, which is unsubstituted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, cyano, nitro, amino, mono-C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylthio, phenyl or phenoxy and in which the phenyl part is unsubstituted or mono to tri-substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆halo-alkoxy, and R is hydrogen or C₁-C₆alkyl. 